Borophosphate

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The borophosphates are mixed anion compounds containing borate and phosphate anions, which may be joined together by a common oxygen atom. Compounds that contain water or hydroxy groups can also be included in the class of compounds. [1]

Contents

Borophosphates can be classified by whether or not they are hydrated, and the anion structure, which can be single, double, triple, isolated ring, isolated branched ring, simple chain, branched chain, loop chain, layers, or three-dimensional network. [1] The isolated anion compounds are the borate phosphates, which contain separate borate and phosphate groups. Some of the borophosphate structures resemble silicates. [1]

Related compounds include aluminophosphates, which have aluminium instead of boron, gallophosphates, [2] with gallium in place of boron, and by substituting the phosphate: boroarsenates, boroantimonates, and vanadoborates.

Formation

Borophosphates can be formed by heating compounds together at up to 900 °C. The products are dense, anhydrous, and do not contain organic substances. [2]

Solvothermal synthesis uses a non water solvent such as ethylene glycol to dissolve the product. [2]

The flux method crystallises from a molten flux of boric acid and sodium dihydrogen phosphate at around 171. [3]

The hydrothermal method heats the ingredients with water under pressure up to 200 °C. The ingredients are boric acid, phosphoric acid, metal salts, or organic bases. Products often contain hydrogen. [2]

The ionothermal synthesis method uses an ionic liquid such as 1-alkyl-3-methylimidazolium bromide as a solvent. This can be done at atmospheric pressure and temperatures under 100 °C. [2]

Characteristics

Borophosphate compounds have been investigated for magnetic, electrical, optical and catalytic properties. Some borophosphates are porous and so have surface for interaction on their interiors, not just their surface. They can reversibly absorb water, or have channels that can allow ions to conduct. The reflection of a labelled tetrahedron cannot be superimposed (even with rotation or movements), so the compounds containing phosphate and borate tetrahedrons can be non-centrosymmetric, or chiral. [2]

List

nameformulacrystal systemspace groupunit cell Åvolumedensitycommentrefs
Li[B3PO6(OH)3]looped chain B3O3 rings OH on B and P [1]
Li2B3PO8P1 [2]
Li3BP2O8P1 [2]
NH4BeBP2O8·⁠1/3⁠H2OcubicP213zeolite-ANA structure [4]
(NH4)2[B3PO7(OH)2]looped chain B3O3 rings OH on B [1]
(NH4)2B2P3O11(OH)monoclinicP21/ca=15.774 b=7.5213 c=8.9661 β=106.93° Z=41020.02.238 [5]
(NH4)3H2[BOB(PO4)3]infinite chains [6]
(NH4)4[H2B2P4O16]tetragonalP41212 [2]
(NH4)2BP2O7(OH)tetragonalP41212a=7.2162 c=14.8258 Z=4772.032.046 [5]
Na2[BP2O7(OH)]orthorhombicPna21a=6.8236, b=20.7911, c=13.1446, Z=12layers [7]
Na3B6PO13orthorhombicPnmaa=9.3727, b=16.2307, c=6.7232, Z=48 member rings [3]
Na3BP2O8monoclinicC2/ca=12.567, b=10.290, c=10.210, β=92.492, Z=2infinite chains [3]
Na5[BOB(PO4)3)]infinite chains [6]
NaBeBP2O8·⁠1/3⁠H2OcubicP213zeolite-ANA structure [4]
Na13(H2O)2[B6P11O42(OH)2]Cl2·H2OF23 [2]
MgBPO4(OH)2P3121 [2]
dimagnesium (monohydrogen­monophosphate­dihydrogenmonoborate­monophosphate)Mg2[BP2O7(OH)3]triclinicP1a=6.452, b=6.455, c=8.360, α=82.50, β=82.56, γ=80.98, Z=1338.8triple [8]
(H3O)Mg(H2O)2[BP2O8]·H2OP6122 [2]
Mg3(H2O)6(B(OH)3PO4)2double [1]
LiMg(H2O)2[BP2O8]·H2OP6522 [2]
NaMg(H2O)2[BP2O8]•H2OhexagonalP6122a=9.428, c=15.820loop branched chain [9]
Na2[MgB3P2O11(OH)]·⁠2/3⁠H2OhexagonalP63a=11.771, c=12.100, Z=62.537colourless [10]
Na3[Al2B6P4O22(OH)3](H2O)6orthorhombicCmcaa=6.9493 b=14.5529 c=24.027 [11]
Na3[Al2BP2O11](H2O)0.5cubicI23a=19.7822 [11]
K2B2P2O9orthorhombicP212121a=7.8227 b=8.1393 c=12.925 Z=4822.92.468 [5]
K2BP2O7(OH)orthorhombicP212121a=7.068 b=7.2396 c=14.116 Z=4722.32.574 [5]
K3B4PO10triclinicP1a=6.546, b=6.567, c=12.930, α=86.04, β=81.40, γ=60.42, Z=2477.92.443colourless 2D sheet [12]
K7B2P5O19 [2]
K3[B5PO10(OH)3]loop branch [1]
LiK2BP2O8P21/n [2]
Li3K2BP4O14Cmca [2]
KBeBP2O8·⁠1/3⁠H2OcubicP213a=12.427, Z=121,919zeolite-ANA structure [4]
K2Na3B2P3O13orthorhombicCmc21a = 13.924 b = 6.7673 c = 12.130 Z = 4B2P3O13 chain [13]
KMg(H2O)2[BP2O8]•H2OhexagonalP6122a=9.463, c=15.815loop branched chain [9]
Ca[BPO5]loop branch B2PO3 rings [1]
Sc(H2O)2[BP2O8]·H2OhexagonalP6522a=9.5752, c=15.8145, Z=61,255.72.378 [14]
Sc(H2O)2[BP2O8]hexagonalP6522a=9.535, c=15.768, Z=6 [14]
NaSc[BP2O6(OH)3]·HPO4P21/c [2]
Ti[BP2O7(OH)3]I41/amd [2]
V2[B(PO4)3] [15]
(VO)2BP2O10 [16]
Li3V2[BP3O12(OH)][HPO4]P21/c [2]
Na2[VB3P2O12(OH)]·2.92H2OI-43m [15]
NH4VIII[BP2O8(OH)]monoclinicP21/ca=9.425, b=8.269, c=9.697, β=102.26°, Z=4738.5 [17]
[ Im H2]3.8(H3O)1.2[(VIVO)4(BO)2(PO4)5]·0.3H2OmonoclinicC2/ca=9.4737, b=22.144, c=17.219, β=105.936°, Z=4layered [18]
[ en H2]2[Na(VO)10B(O)2(OPO3H)2}5]·22.5H2O [19]
[ trien H4]4H[NH4(VO)12{B(O)2(OPO3)2}6]·14H2OorthorhombicPbcaa=21.45, b=16.315, c=29.65, Z=4103781.920 [20]
[ trien H4]4H[K(VO)12{O3POB(O)2OPO3}6]·16H2OorthorhombicPbcaa=21.537, b=16.267, c=29.717, Z=4104111.996 [20]
KV[BP2O8(OH)]triclinicP1 [2]
Cr2[B(PO4)3]P63/m [15]
Na{Cr[BP2O7(OH)3]}monoclinicC2/ca=10.4220, b=8.2468, c=9.2053, β=116.568°, Z=4707.63 [21]
Na8[Cr4B12P8O44(OH)4][P2O7]·nH2OI23 [2]
Na11K5[NaCr8B4P12O60H8]·H2OPmnn [2]
H2Mn5(H2O)6[BP2O8]4•4H2OhexagonalP6122a=9.655, c=15.791, Z=1.5pale pink [22]
Mn[BPO4(OH)2]P3221a=7.5750, c=12.927, Z=6642.373.020 [23]
LiMn(H2O)2[BP2O8(OH)]·H2OP6522 [2]
(NH4)Mn(H2O)2(BP2O8)·H2OP6522a = 9.6559, c = 15.79391275.3 [24]
[NH4]4[Mn9B2(OH)2(HPO4)4(PO4)6]monoclinicC2/ca=32.603, b=10.617, c=10.718, β=108.26°, Z=435232.971light pink [25]
(NH4)6[Mn3B6P9O36(OH)3]·4H2OC2 [2]
(NH4)7Mn4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4]Pnma [2]
(C3H12N2)[MnB2P3O12(OH)] [2]
(C4H12N2)[MnB2P3O12(OH)]Ima2 [2]
NaMn(H2O)2[BP2O8]•H2OhexagonalP6122a=9.589, c=15.939loop branched chain [9]
Na5(H3O){Mn3[B3O3(OH)]3(PO4)6}·2H2OhexagonalP63/ma=11.9683, c=12.1303, Z=2 [26]
Na5(NH4)Mn3[B9P2O33(OH)3]·⁠3/2⁠H2OP63 [2]
Na2[MnB3P2O11(OH)]·⁠2/3⁠H2OhexagonalP63a=11.940, c=12.098, Z=62.670colourless [10]
KMnBP2O7(OH)2monoclinicP21/ca=6.659, b=12.049, c=9.790, β=109.12°, Z=4742.2orange-red luminescence [27]
KMn(H2O)2[BP2O8]•H2OhexagonalP6122a=9.639, c=15.931loop branched chain [9]
K5Mn2B2P5O19(OH)2P21/n [2]
FeIII2[B(PO4)3]P63/m [15]
Fe[B2P2O7(OH)5]monoclinicC2/ca=17.745, b=6.720, c=7.059, β=109.01°, Z=47962.808unbranched chain [1]
Fe(H2O)2BP2O8·H2Ohexagonala=9.4583, c=15.707, Z=61216.92.543 [28]
Fe[BPO4(OH)2]P3221a=7.4844, c=12.844, Z=6623.063.129 [23]
FeII(H2O)2[B2P2O8(OH)2]·H2OP21/c [2]
Fe1.834IIFe0.166IIIB0.5[PO3(OH)]0.8(HPO3)2.033cubicI43da=21.261, Z=48 [29]
NH4FeIII[BP2O8(OH)]monoclinicP21/ca=9.393, b=8.285, c=9.689, β=102.07°, Z=4737.4 [17]
(NH4)0.75Fe(H2O)2[BP2O8]·⁠1/4⁠H2OP6522 [2]
(C3H12N2)[FeB2P3O12(OH)]Ima2 [2]
(C4H12N2)[FeB2P3O12(OH)]Ima2 [2]
(dienH3)(dienH2)0.5[FeII*III2B4P7O26(OH)4]P1 [2]
NaFe[BP2O7(OH)3]triple
sodium diaquoiron(II) catena-[monoboro-diphosphate] monohydrateNaFe(H2O)2[BP2O8]•H2OhexagonalP6122a=9.499, c=15.931loop branched chain [9]
Na2[FeB3P2O11(OH)]·⁠2/3⁠H2OhexagonalP63a=11.812, c=12.067, Z=62.742light yellow [10]
potassium diaquoiron(II) catena-[monoboro-diphosphate] hemihydrateKFe(H2O)2[BP2O8]•H2OhexagonalP6122a=9.510, c=15.952loop branched chain [9]
K2Fe2[B2P4O16(OH)2]monoclinicP21/ca=9.372, b=8.146, c=9.587, β=101.18°, Z=2718.0B2P2O4 ring with phosphate sides [30]
KFeBP2O8(OH)P21/c [2]
CaFe[BP2O7(OH)3]C2/c [2]
Ca0.5Fe(H2O)2[BP2O8]·H2OP6522 [2]
Co5[BP3O14]double + phosphate [1]
Co3[BPO7]monoclinicCma=9.774, b=12.688, c=4.9057, β=119.749°, Z=4528.2 [31]
Co[BPO4(OH)2]P3121a=7.4554, c=12.7397, Z=6613.243.229 [23]
(NH4)7Co4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4]Pnma [2]
(NH4)8[Co2B4P8O30(OH)4]P1 [2]
(NH4)Co(H2O)2(BP2O8)·H2OP6122a = 9.501 c = 15.5821218.2 [24]
CoII(H2O)2[B2P2O8(OH)2]·H2OP21/c [2]
[Co(en)3][B2P3O11(OH)2] [32]
CoB2P3O12(OH)·H2 en [33]
Co(C4H12N2)[B2P3O12(OH)]orthorhombicIma2a=12.4635, b=9.4021, c=11.4513, Z=41341.90 [34]
H2Co5(H2O)6[BP2O8]4•4H2OhexagonalP6122a=9.639, c=15.931, Z=1.5purple
LiCo(H2O)2[BP2O8]·H2OP6522
NaCo(H2O)2[BP2O8]•H2OhexagonalP6122a=9.455, c=15.847loop branched chain [9]
NaCoH2BP2O9monoclinicP21/ca=6.547, b=11.404, c=9.650, β=107.37687.62.905pink; discovered in Tunisia [35]
Na2[CoB3P2O11(OH)]·⁠2/3⁠H2OhexagonalP63a=11.759, c=12.099, Z=62.781purple [10]
Na5(H3O){Co3[B3O3(OH)]3(PO4)6}·2H2OhexagonalP63/ma=11.7691, c=12.112, Z=2 [26]
Na6Co3B2P5O21Cl·H2OPnma
KCo(H2O)2[BP2O8]•H2OhexagonalP6122a=9.483, c=15.827loop branched chain [9]
CaCo(H2O)[BP2O8(OH)]·H2OP1 [2]
(K0.17Ca0.42)Co(H2O)2[BP2O8]·H2OP6522 [2]
(Co0.6Mn0.4)2(H2O)[BP3O9(OH)4]P212121 [2]
cobalt borophosphate ethylenediamineCoB2P3O12(OH)·en orthorhombicPbcaa=9.3501, b=12.2426, c=20.8802,390.12.471purple; layered [36] [37]
(NH4)7Co4(H2O)[B2P4O15(OH)2]2[H2PO4][HPO4]OrthorhombicPnmaa=16.9206, b=10.5592, c=22.000, Z=43,930.62.386pink [38]
(NH4)2(C4H12N2)[Co2B4P6O24(OH)2]·H2OI41/a [2]
NiBPO4(OH)2P3121 [2]
Ni(H2O)2[B2P2O8(OH)2]·H2OP21/c [2]
LiNi(H2O)2[BP2O8]·H2OP6522 [2]
NaNi(H2O)2[BP2O8]•H2OhexagonalP6122a=9.371, c=15.831loop branched chain [9]
Na2[NiB3P2O11(OH)]·⁠2/3⁠H2OhexagonalP63a=11.728, c=12.074, Z=62.799yellow [10]
Na5(H3O){Ni3[B3O3(OH)]3(PO4)6}·2H2OhexagonalP63/ma=11.7171, c=12.0759, Z=2 [26]
KNi(H2O)2[BP2O8]•H2OhexagonalP6122a=9.392, c=15.842loop branched chain [9]
Cu3[B2P3O12(OH)3]monoclinicCca=6.1895, b=13.6209, c=11.9373, β=97.62°, Z=4997.5 [39]
Cu(H2O)2[B2P2O8(OH)2] [40]
Cu2(H2O)[BP2O8(OH)]Pbca [2]
LiCu2[BP2O8(OH)2]C2/c [2]
LiCu2[BP2O8(OH)2]P212121 [2]
Na2[CuB3P2O11(OH)]·⁠2/3⁠H2OhexagonalP63a=11.554, c=12.314, Z=62.862sky-blue [10]
Na4Cu3[B2P4O15(OH)2]•2HPO4ring with side phosphate and extra phosphate
Na5KCu3[B9P6O33(OH)3]·H2OP63/m [2]
Zn(C4H12N2)[B2P3O12(OH)]orthorhombicIma2a=12.4110, b=9.4550, c=11.4592, Z=41344.69 [34]
lithium zinc diaqua catena-[monoboro-diphosphate]-monohydrateLiZn(H2O)2[BP2O8] · H2OhexagonalP61a=9.469, c=15.667, Z=61216.6spiral ribbons [41]
Na[ZnBP2O8]⋅H2OhexagonalP6122a=9.5404, c=14.7780, Z=61164.88 [42]
NaZn(H2O)2[BP2O8]•H2OhexagonalP6122a=9.456, c=15.828loop branched chain [9]
Na2[ZnB3P2O11(OH)]·⁠2/3⁠H2OhexagonalP63a=11.963, c=12.363, Z=62.683colourless [10]
NH4[ZnBP2O8]triclinicP1a=7.437, b=7.612, c=7.850, α=119.05, β=101.59, γ=103.43, Z=2351.182.687 [43]
Na[ZnBP2O8]triclinicP1 [2]
K[ZnBP2O8]monoclinicC2/ca=12.617, b=12.773, c=8.415, β=91.25°, Z=81355.82.991 [43]
[ trien H4]1.5[Zn6B6P12O48]·⁠3/2⁠H2OhexagonalP6522a=9.6685, c=14.8879; Z=1 [44]
RBPORb3B11P2O23TriclinicP1a=7.785, b=7.839, c=7.963, α=89,774, β=89.129, γ=88.211, Z=2485.62.753transparent above 168 nm; SHG 2.5× KDP; birefringence =0.071@1064 nm [45]
Rb[P2B2O8(OH)]network [1]
Li3Rb2BP4O14Cmca [2]
Rb3B11PO19F3trigonalR3a=11.3715 c=12.0240 Z=31346.532.839colourless; decompose > 470 °C; SHG 1.3 × KDP [46]
K2RbB4PO10triclinicP1a=6.5577, b=6.5931, c=13.098, α=84.626, β=80.514, γ=60.457, Z=2485.92.719colourless [12]
K2RbB8PO16birefringence 0.057@1064 nm [47]
K0.9Rb2.1B8PO16monoclinicCca=11.3446 b=6.5485 c=19.354 β=101.315°1409.92.761birefringence 0.075@532 nm; band gap 6.16 eV;SHG 0.7 × KDP [48]
Rb2Co3(H2O)2[B4P6O24(OH)2]orthorhombicPbcaa = 9.501, b = 12.272, c = 20.074, Z = 4 [49]
Rb[ZnBP2O8]triclinicP1a=7.439, b=7.639, c=7.861, α=118.82, β=101.73, γ=103.51, Z=2353.43.304 [43]
Sr[BPO5]P3221loop branch B2PO3 rings [1]
KSrBP2O8I42da=7.109, c=13.882 [50]
SrFe[BP2O8(OH)2]C2/c [2]
SrCo2BPO7monoclinicP21/ca=6.485, b=9.270, c=10.066, β=111.14, Z=4548.7red [51]
AgMg(H2O)2[BP2O8]·H2OP6522 [2]
⁠2/3⁠H2OP6522 [2]
(Ag0.57Ni0.22)Ni(H2O)2[BP2O8]·⁠2/3⁠H2OP6522 [2]
Na3Cd3BP4O16orthorhombicPmc21a=13.6854, b=5.335, c=18.2169, Z=4SHG 1.1×KDP [2] [52]
NH4Cd(H2O)2(BP2O8)·0.72H2OhexagonalP65a=9.698, c=16.026, Z=61305.32.886colourless [53]
In2[B(PO4)3]P63/m [15]
Cs[P2B2O8(OH)]3D network [1]
Li2Cs2B2P4O15
K2CsB4PO10triclinicP1a=6.6235, b=6.6243, c=13.273, α=79.734, β=86.558, γ=60.095, Z=2496.462.979colourless [12]
Cs2Cr3(BP4O14)(P4O13)monoclinicP21/ca=14.7918, b=15.819, c=9.7037, β=92.450, Z=4876.93.257green; [B(P2O7)2]5− [54]
CsFe(BP3O11)orthorhombicPnmaa=8.5375, b=12.7829, c=8.3346, Z=4909.593.434[N(PO4)(P2O7)]4- [54]
Cs2Co3(H2O)2[B4P6O24(OH)2]orthorhombicPbcaa=9.5526, b=12.3190, c=20.11232366.8pink [2] [55]
Cs[ZnBP2O8]triclinicP1a=7.506, b=7.914, c=8.038, α=1198.05, β=102.96, γ=104.50, Z=2373.93.545 [43]
Ba[BPO5]P3221 [2]
Ba[BP3O12]orthorhombicIbcaa=7.066, b=14.268, c=22.1592233.94.209 [1] [56]
BaB2P2O8F2monoclinicP21/na=4.4719 b=20.499 c=7.8896 β=92.955° Z=4722.33.558birefringence 0.007 @ 532 nm
KBaBP2O8I42da=7.202, c=14.300 [50]
BaFe[BP2O8(OH)]P1 [2]
BaCo[BP2O8(OH)]P1 [2]
Pb[BPO5]loop branch B2PO3 rings [1]
Pb3[(PO4)2BPO4]orthorhombicPbcaa=6.946, b=14.199, c=21.116, Z=82082.55.851open branch, 2 PO4 extra on each B [56]
Na3PbII[B(O3POH)4]I41/a [2]
KPbBP2O8I42d [2]
PbII4Cl{Co2[B(OH)2P2O8](PO4)2]}R3c [2]
RbPbBP2O8I42d [2]
BiCo2BP2O10P21/m [2]
BiNi2BP2O10P21/m [2]
K2(UO2)12[B(H2PO4)4](PO4)8(OH)(H2O)6tetragonalI42ma=21.8747, c=7.06523380.7 [57]
K5(UO2)2[B2P3O12(OH)]2(OH)(H2O)2monoclinicP21a=6.7623, b=19.5584, c=11.0110, β=95.579°1449.42 [57]
Ag2(NH4)3{(UO2)2[B3O(PO4)4(HPO4)2]}·H2OP1 [2]
Ag2−x(NH4)3{(UO2)2[B2P5−yAsyO20−x(OH)x]}Pcmn [2]
Cs3(UO2)3[B(PO4)4]∙(H2O)0.5P41212a=12.2376, c=33.9468, Z=45083.8yellow; microporous [58]

References

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  5. 1 2 3 4 Yang, Xia; Zhang, Wenbin; Pan, Xueting; Hou, Xueling; Han, Shujuan (2023-11-22). "Hydroxyl-Driven Enhanced Birefringence in Borophosphates". Inorganic Chemistry. 62 (49): 20430–20438. doi:10.1021/acs.inorgchem.3c03394. ISSN   0020-1669. PMID   37992320. S2CID   265380309.
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  8. ↑ Häuf, C.; Boy, I.; Kniep, R. (1999-03-01). "Crystal structure of dimagnesium (monohydrogenmonophosphate-dihydrogenmonoborate-monophosphate), Mg2[BP2O7(OH)3]". Zeitschrift für Kristallographie - New Crystal Structures. 214 (1): 3–4. doi: 10.1515/ncrs-1999-0103 . ISSN   2197-4578. S2CID   97517209.
  9. 1 2 3 4 5 6 7 8 9 10 11 Kniep, Rüdiger; Will, Horst Günter; Boy, Insan; Röhr, Caroline (1997). "61 Helices from Tetrahedral Ribbons ∞
    1    [BP2O3−
    8    ]: Isostructural Borophosphates MIMII(H2O)2[BP2O8] · H2O (MI=Na, K; MII=Mg, Mn, Fe, Co, Ni, Zn) and Their Dehydration to Microporous Phases MIMII(H2O)[BP2O8]"    . Angewandte Chemie International Edition in English. 36 (9): 1013–1014. doi:10.1002/anie.199710131. ISSN   1521-3773.
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